终缩聚反应温度对聚酯品质的影响

分析了在终缩聚反应中温度对聚酯的黏度、色相、二甘醇含量和熔点的影响,得出了终缩聚反应的最佳温度控制范围。终缩聚反应的更好温度为283~287℃,最佳温度为285℃。     

有机蒙脱土对PET后缩聚反应的影响

实验研究了有机蒙脱土对PET后缩聚反应过程的影响。结果表明有机蒙脱土对PET缩聚反应的前期有加速作用，但由于对气液传质过程有阻碍作用，导致了PET后缩聚反应的速度下降。蒙脱土的存在还使缩聚过程中二甘醇(DEG)基团及端羧基基团浓度上升。根据缩聚反应机理建立了PET后缩聚过程的数学模型，并依据实验结果拟合出缩聚反应动力学参数及气液传质系数。模型计算结果能较好地反映PET后缩聚过程中特性粘数的变化及DEG基团的生成规律，但对端羧基浓度的变化存在较大的偏差。     

羰基硫在二乙二醇二乙醚/水二元混合体系中的水解

The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl ether enhances the solubility and hydrolysis rate of carbonyl sulfide compared with that in pure water. The composition of the mixture with maximum hydrolysis rate varies with temperature. The thermophysical properties including density, viscosity, and surface tension as a function of composition at 20℃ under atmospheric pressure as well as liquid-liquid equilibrium (LLE) data over the temperature range from 28℃ to 90℃ are also measured for the binary mixture.     

规模化聚酯装置酯化过程的机理模型化

聚对苯二甲酸乙二醇酯(PET)酯化反应体系的热力学物性计算、动力学常数的整定是实现聚酯工业生产装置模型化的2个重要部分。对聚酯酯化过程的各主副反应——酯化反应、缩聚反应、水解反应、醇解反应、二甘醇生成反应进行机理分析和参数比较,确定了聚酯生产全流程模拟的动力学常数的合理范围。通过动力学参数对目标产物对苯二甲酸、二甘醇、乙二醇、PET质量流量影响的灵敏度分析,修正了反应动力学常数使之适应特定的工业装置,结合物性计算方程建立了规模化聚酯装置酯化工段的机理型数学模型。利用不同生产负荷的工业数据对模型进行了验证,其误差在3%以内。     

新戊二醇改性PET的合成研究

以对苯二甲酸（PTA）、乙二醇（EG）为主要原料,添加第三单体新戊二醇（NPG）合成了一系列不同NPG含量的共聚酯（PENT）,研究了NPG对酯化、缩聚过程的影响,分析了PENT共聚酯的常规性能。结果表明,酯化反应速率和聚合反应速率随NPG含量的增加而下降,共聚酯中的二甘醇（DEG）含量和端羧基（CEG）含量随NPG含...     

不饱和脂肪族聚酯生物降解性的研究

以1，4-反丁烯二酸和一缩二乙二醇（DEG）为原料，采用缩聚法合成端羟基不饱和聚酯，并采用红外光谱分析（FT—IR）、羟值、酸值、黏度等对所得聚合物进行表征，确认了其分子结构．对其降解性进行研究，并且与1，4-丁二酸与一缩二乙二醇合成的饱和脂肪族聚酯进行了对比。研究结果表明，不饱和脂肪族聚酯和饱和脂肪族聚酯的生物降解性差别不大，也就是双键的引入对其生物降解性没有大的影响；但是不饱和脂肪族聚酯膜经过高温处理后，双键会打开发生交联，而交联后的不饱和脂肪族聚酯的生物降解性变差，而且交联度越高，生物降解性越差。     

PET synthesis in the presence of new aluminum catalysts

A new polycondensation catalyst (ethylene glycol aluminum) was synthesized and applied in PET synthesis. It has been characterized by spectral studies (IR, NMR). The catalytic activity of organic aluminum compound was discussed in this paper. In this investigation, the synthesis of poly(ethylene terephthalate) (PET) is presented using ethylene glycol (EG) and terephthalic acid (TPA). The result proved that ethylene glycol aluminum was the real catalytic material. And it was proved to be the most efficient catalyst for the polycondesation reaction among the organic aluminum compounds. Similar catalytic activity has been observed for ethylene glycol aluminum compared to ethylene glycol antimony. The esterification reaction was monitored by measuring the distilled water as a function of time and the modeling of this process was carried out from these data. The received PET samples were characterized by viscometry, carboxyl end-group content and diethylene glycol (DEG) content. A mechanism of aluminum catalysis has been proposed to explain these observations.     

β-二酮铝和β-二酮酯铝催化合成聚对苯二甲酸乙二醇酯

采用对苯二甲酸(TPA)和乙二醇(EG)为原料,以自制的β-二酮铝和β-二酮酯铝为催化剂经酯化、缩聚,制得聚对苯二甲酸乙二醇酯(PET).探讨了反应条件对合成反应的影响.结果表明:β-二酮酯铝和乙酰丙酮铝优于其他β-二酮铝.EG与TPA的摩尔比为1.2∶1、催化剂的用量为0.5%(与TPA的摩尔比),酯化反应温度为26...     

桐油改性双环戊二烯不饱和树脂的合成研究

利用缩聚反应后期桐油与双环戊二烯不饱和聚酯(DCPD-UPR)主链上不饱和双键的Diels-Alder(D-A)反应合成了桐油改性DCPD-UPR,研究了各种原料用量对桐油改性DCPD-UPR其浇注体力学性能的影响。结果表明:当顺酐与苯酐的物质的量比为2∶1～3∶1,双环戊二烯与顺酐物质的量比为0.6～0.8∶1,1,2-丙二醇与二甘醇物质的量比2∶1,缩聚反应后期加入10%(质量分数)桐油,苯乙烯质量分数为35%～40%时,获得的桐油改性DCPD-UPR粘度适中,浇注体的断裂伸长率提高了78.2%,冲击强度提高了82.0%。     

Synthesis and Physicochemical Studies of Some Novel Homopolyesters Based on s-Triazine

The diacid chloride 2-(N-methyl piperazine)-4,6-bis(2-naphthoxy-6-carbonyl chloride) [MPNCCT] has been synthesized, from which different homopolyesters have been made by polycondensation with the following diols: bisphenol-A [BPA], bisphenol-C [BPC], bisphenol-S [BPS], 1,4-dihydroxy anthraquinone [1,4-DHA], 1,8-dihydroxy anthraquinone [1,8-DHA], catechol [C], resorcinol [R], phenolphthalein [Ph], ethylene glycol [EG] and diethylene glycol [DEG]. All the synthesized polyesters were characterized by solubility, density, viscosity measurements, IR spectra, NMR spectra and thermogravimetric analysis [TGA].     

高固含量水性羟基聚丙烯酸酯的制备研究

实验以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、苯乙烯(St)、丙烯酸(AA)、丙烯酸羟丙酯(HPA)、过氧化苯甲酰(BPO)、叔丁基过氧化物、链转移剂、二甲基乙醇胺(DMAE)、丙二醇甲醚(PM)、一缩二乙二醇丁醚为主要原料,溶液聚合法合成了含羟基水性聚丙烯酸酯树脂,将合成树脂固含量控制在80%~85%,水分散体固含量为45%,黏度小于1 500 mPa.s。讨论了引发剂、链转移剂、引发温度、玻璃化转变温度等因素对树脂合成及水分散体黏度的影响。研究结果表明:随着引发剂、链转移剂用量的增加,合成树脂及分散体黏度降低;随着引发温度的提高,合成树脂及水分散体黏度下降;玻璃化转变温度越高,合成树脂黏度越低。     

不同间苯含量的共聚酯的合成

研究了 Ti和 Sb催化下不同的间苯含量的共聚酯 (PEIT)的酯化、缩聚反应。结果表明 :随着间苯含量的增加 ,PEIT的酯化反应诱导期缩短 ,酯化温度降低 ,缩聚反应诱导期增长。Ti催化的 PEIT酯化反应速率高于 Sb,而且缩聚反应诱导期比 Sb明显缩短。     

五釜工艺聚酯工业装置的稳态模拟

针对大型连续PTA直接酯化法PET工艺过程装置,以Aspen Plus和Polymers Plus为模型开发工具,建立了以反应和传质过程机理为基础的稳态模型。结果表明:该模型中包括了酯化反应、缩聚反应、二甘醇生成反应、链降解反应和乙醛生成等主副反应,且考虑了端羧基对酯化反应的自催化效应;更重要的是模型考虑了酯化阶段PTA在酯化反应器中的溶解过程和终缩聚阶段小分子的脱挥,并建立了小分子脱挥的传质系数与缩聚反应器内聚合度、黏度、温度和搅拌器转速等的关联;在此模型基础上模拟研究了第一酯化反应操作温度对各反应器出口指标的影响,指出酯化段的酯化率有一个适宜的控制范围。     

Preparation and characterization of high initial bonding strength reactive hot melt polyurethane adhesive derived from phthalate polyester polyols

A series of phthalate polyester polyols (PEs) were synthesized via a polycondensation reaction with phthalic anhydride (PA) and different glycols, such as neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), 2-methy-1,3-propanediol (MPO), 1,4-butylene glycol (1,4-BDO) and trimethylolpropane (TMP). Reactive hot melt polyurethane adhesive (HMPUR) with high initial bonding strength was then prepared by poly(propylene glycol) 2000 (PPG-2000), Dynacoll 7360 with these resultant PEs. Effects of different glycols on the glass transition temperature (T_g) and viscosity of the PEs were investigated. Besides, influences of these resultant PEs on the water resistance, bonding strength, thermal stability and surface morphology of the HMPUR were further discussed. The experimental results showed that T_g and viscosity of the PEs decreased with the increase of the chain flexibility of diols. The initial bonding strength of the HMPUR increased with the increase of T_g of the PEs. The hydrogen bonds and cross-linking structure of the HMPUR will also lead to the increase of the bonding strength. In addition, the water resistance of HMPUR was improved by the cross-linking structure and lateral methyl groups of the PEs, while the thermal stability changed little. The surface morphology of the HMPUR showed that all samples have two phase structures and the HMPUR based on DEG and 1,4-BDO exhibited weak phase separation.     

环保增塑剂二甘醇二苯甲酸酯的合成研究

在对甲苯磺酸催化下、使用环己烷作带水剂,以苯甲酸和二甘醇为原料合成环保增塑剂二甘醇二苯甲酸酯（DEDB）。研究考察了酸醇摩尔比、催化剂用量、带水剂用量和反应时间等因素对产率的影响。确定了最佳工艺条件：n（苯甲酸）∶n（二甘醇）=2.0∶1.1、催化剂用量（以苯甲酸的摩尔数计）3.0%、环己烷12 mL、回流反应时间8 h,目标产品的产率为98.0%。     

六水氯化镁在六种多元醇中溶解度的测定和关联

六水氯化镁的溶解度是镁盐综合利用的重要基础数据。采用静态平衡法测定了六水氯化镁在1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、一缩二乙二醇、二缩三乙二醇、一缩二丙二醇6种多元醇中的溶解度（278.15~328.15 K）。实验结果表明,六水氯化镁在6种多元醇中的溶解度均随着温度的升高而增大,其中在一缩二乙二醇中的溶解度最大,在二缩三乙二醇中的溶解度随着温度的变化较其他多元醇变化更为明显。使用Apelblat方程、λh方程、Van′t Hoff方程和多项式方程对溶解度数据进行了关联,结果良好,其中Apelblat方程和多项式方程拟合结果优于其他方程。利用Van′t Hoff方程计算了6种体系的溶解焓、溶解熵和吉布斯自由能。这些结果对镁盐的分离提取及镁基功能材料的制备具有重要的参考价值。     

Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.     

Ti系催化剂对纤维级PET切片质量影响的研究

采用不同含量的Ti系催化剂制备了纺丝用聚对苯二甲酸乙二醇酯（PET）切片,通过乌氏黏度仪、差式扫描量热仪（DSC）、色差仪、气相色谱等仪器测试了影响PET切片质量的性能指标,包括特性黏度、熔点、色相（L值、b值、a值）、端羧基含量、二甘醇和间苯二甲酸（1PA）含量。结果表明,Ti系催化剂的含量对纺丝用PET切片的质量有很大影响,尤其是对色相b值的影响比较大。     

常压下二乙二醇单乙醚和水二元体系不同温度下的密度、黏度及过量性质

Densities and viscosities were measured as a function of composition for binary liquid mixture of diethylene glycol monoethyl ether [CH3CH2O(CH2)2O(CH2)2OH] + water from 293.15 to 333.15 K at atmospheric pressure, with a capillary pycnometer and Ubbelohde capillary viscometer respectively. From the experimental data, the excess molar volume VE, viscosity deviation η, and the excess energy of activation for viscous flow G*E were calculated. These data were correlated by the Redlich-Kister type equa-tions to obtain the coefficients and standard deviations. The results showed a strong molecular interaction between diethylene glycol monoethyl ether and water.     

Optimization of the polycondensation stage of poly(ethylene terephthalate) reactors

A general kinetic scheme for the polycondensation step of the PET formation has been used to establish the mole balance equations of various functional groups in batch reactors. An objective function has been defined which aims to attain a desired degree of polymerization in the shortest time, has a specified level of diethylene glycol group content, and minimizes the other side products. Using the control vector iteration procedure, an optimum temperature profile has been calculated. The computations suggest that a high temperature should be used initially which must be lowered as the time of reaction increases for limiting the formation of side products.